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Published on: February 27, 2017
Origin of Ferroelectricity in Two Prototypical Hybrid Organic-Inorganic Perovskites
Kai Li1, Zhi-Gang Li1, Jun Xu1
1School of Materials Science and Engineering & Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300350, China.
Abstract:
Hybrid organic-inorganic perovskite (HOIP) ferroelectrics are attracting considerable interest because of their high performance, ease of synthesis, and lightweight. However, the intrinsic thermodynamic origins of their ferroelectric transitions remain insufficiently understood. Here, we identify the nature of the ferroelectric phase transitions in displacive [(CH3)2NH2][Mn(N3)3] and order-disorder type [(CH3)2NH2][Mn(HCOO)3] via spatially resolved structural analysis and ab initio lattice dynamics calculations. Our results demonstrate that the vibrational entropy change of the extended perovskite lattice drives the ferroelectric transition in the former and also contributes importantly to that of the latter along with the rotational entropy change of the A-site. This finding not only reveals the delicate atomic dynamics in ferroelectric HOIPs but also highlights that both the local and extended fluctuation of the hybrid perovskite lattice can be manipulated for creating ferroelectricity by taking advantages of their abundant atomic, electronic, and phononic degrees of freedom.
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